Monomeric emulsion stabilizers derived from alkyl/alkenyl succinic anhydride

ABSTRACT

1. A COMPOUND HAVING THE FORMULA   V-R&#39;&#39;-N(+)(-R1)(-R2)-R&#34;-A-CO-CH(-R3)-CH2-COOH X(-)   OR   V-R&#39;&#39;-N(+)(-R1)(-R2)-R&#34;-A-CO-CH2-CH(-R3)-COOH X(-)   WHEREIN V IS AN ETHYLENICALLY UNSATURATED RADICAL SELECTED FROM THE GROUP CONSISTING OF ACRYLOYLOXY, METHACRYLOYLOXY, ACRYLAMIDO, METHACRYLAMIDO, VINYLOXY, ALLYLOXY, METHALLYLOXY, 4-HYDROXYMALEOYLOXY, 4-HYDROXYFUMAROYLOXY, 4-HYDROXYCITRACONYLOXY OR 4-HYDROXYITACONYLOXY; R&#39;&#39; AND R&#39;&#39;&#39;&#39; ARE INDEPENDENTLY SELECTED ETHYLENE, PROPYLENE ISOPROPYLENE, 2-HYDROXYPROPYLENE, ACETOXYPROPYLENE OR -O-CH2-CHR4(O-CH2-CHR4)N WHERE N IS ZERO TO 4 AND R4 IS HYDROGEN OR METHYK; A IS OXYGEN; R1 AND R2 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING 1 TO 7 CARBON ATOMS, HYDROXYALKYL HAVING 1 TO 7 CARBON ATOMS OR BENZYL; R3 IS A LIPOPHILIC ALIPHATIC HYDROCARBON GROUP HAVING FROM 7 TO 28 CARBON ATOMS, AND X- IS HALIDE OR TOLUENE SULFONATE.

3,839,419 MONOMERIC EMULSION STABILIZERS DE- RIVED FROM ALKYL/ALKENYLSUCCINIC ANHYDRIDE Carlos M. Samour, Wellesley, and Mildred C. Richards,Wakefield, Mass., assignors to The Kendall Company No Drawing.Application May 26, 1970, Ser. No. 40,718,

now Patent No. 3,751,451, which is a continuation-inpart of abandonedapplication Ser. No. 867,900, Oct. 20, 1969. Divided and thisapplication Nov. 24, 1972, Ser. No. 309,038

Int. Cl. C07c 69/40 US. Cl. 260-485 H Claims ABSTRACT OF THE DISCLOSUREQuaternary ammonium salts having a lipophilic group covalently linked tothe quaternary nitrogen through hydroxysuccinyloxy orhydroxysuccinylamino radicals are disclosed. These quaternary ammoniumsalts are useful as monomeric emulsion stabilizers.

This is a divisional of application Ser. No. 40,718, filed May 26, 1970,now US. Pat. 3,751,451, which is a continuation-in-part of copendingapplication Ser. No. 867,900, filed Oct. 20, 1969, now abandoned.

This invention relates to stabilizing agents for emulsionpolymerization. More particularly it relates to a class of quaternizedorganic salts which serve simultaneously as stabilizing agents foremulsion polymerizations and as monomeric reactants in thepolymerization, so that the salts become an integral part of thepolymer, which is thereby self-stabilized without the use ofsurfactants.

Polymeric latices, derived from ethylenically-unsaturated monomers, arewidely used for a variety of applications, such as adhesive masses andbinders for non woven fabrics. Most conventional polymeric latices areproduced by an emulsion polymerization process, in which monomericmaterials are polymerized while they are dispersed in an aqueous mediumby means of a surface active agent. The surface active agent may beanionic in nature, such as soap or sodium lauryl sulfate. Alternatively,it may be of a nonionic type as represented by various ethylene oxidederivatives, or by polyhydroxy compounds, or it may be cationic, asrepresented by alkyl ammonium halides. Cationic agents are preferablycombined with a nonionic agent for improved performance. Thepolymerization of monomeric materials is also frequently effected in thepresence of water-soluble protective colloids or stabilizing agents. Anyof the above emulsifying or stabilizing agents leads to the presence ofa water-sensitive ingredient in the final polymeric latex. For latexutilizations wherein wet strength and resistance to the influence ofwater are desirable, as in most paper coatings, nonwoven fabrics,certain pressure-sensitive adhesive tapes, and the like, the presence ofa water-sensitive ingredient in the polymeric mass is undesirable.

-A preferred method of avoiding the presence of watersensitive elementsin a polymeric latex is to employ what is termed herein monomericemulsion stabilizers-that is, a class of organic monomer whichco-polymerizes with the ethylenically-unsaturated monomers, becoming apart of the final polymer, but which stabilizes the polymerizationprocess against the formation of coagulum and against subsequent phaseseparation. Such monomeric emulsion stabilizers may becationically-charged nitrogen compounds as set forth in US. Pat. No.3,399,159 wherein the use of monomers such as vinyl pyridines,acidamines, and certain nitrogen-containing acrylic derivatives isdescribed.

United States Patent 0 Now it has been found that selected quaternaryammonium salts wherein the quaternized nitrogen is covalently linked toa lipophilic group through a hydroxysuccinyloxy or hydroxysuccinylaminogroup are excellent monomeric emulsion stabilizers for thepolymerization of ethylenically-unsaturated monomers.

More particularly, the compounds of this invention have the formulawherein V is an ethylenically-unsaturated radical; R is zero or adiradical; R" is a diradical; A is oxygen or NH-; R and R areindependently selected alkyl, hydroxyalkyl, aryl, R OCO-CH or wherein Ris hydrogen or alkyl or together part of a heterocyclic amino radical inwhich the quaternary nitrogen atom in formula I is part of the ring; Ris a lipophilic radical comprising an aliphatic hydrocarbon group havingabout 7 to about 28 carbon atoms; and X- is a halide, alkyl sulfatewherein the alkyl moiety has 1 to 4 carbon atoms or toluene sulfonateradical. Isomers of compounds I wherein the lipophilic radical R isattached to the carbon atom adjacent to the carboxyl group are alsoincluded in the scope of this invention.

These compounds I are readily prepared from available materials, andthus are attractive for use in commercial operations.

While any compound having the general formula I can be providedaccording to this invention, preferred monomeric emulsion stabilizersinclude these compounds I where V is an ethylenically-unsaturatedradical selected from the group consisting of acryloyloxy,methacryloyloxy,

acrylamido, methacrylamido, vinyloxy, allyloxy, methallyloxy,vinylacetoxy, allylacetoxy, methallylacetoxy, allyl, methallyl, and acidester groups or acid amido groups such as 4-hydroxymaleoyloxy and4-hydroxyfumaroyloxy (HOCO-CH=CHCOO), 4-hydroxymaleoylamino and 4hydroxyfumaroylarnino (HOCOCI-I:=CHCONH), 4 hydroxycitraconyloxy(HOCO-CH=C(CH )-COO), 4-hydroxycitraconoylamino (HO-COCH=C(CH )-CONH-),4-hydroxyitaconoyloxy HOCOCH2CCOO- iJHz and 4-hydroxyitaconoylaminoHOCOOHzC-CONH CH2 R and R" are independently selected ethylene,propylene, isopropylene, Z-hydroxypropylene, acetoxypropylene or OCH CHR(OCH CHR.,,) where n is zero to 4 and R is hydrogen or methyl; with theproviso that R is Zero Where V is vinylacetoxy, allylacetoxy,methallylacetoxy, allyl, or methallyl;

A is oxygen or -NH-;

R and R are a. independently selected from the group consisting of alkylhaving 1 to 7 carbon atoms, hydroxyalkyl having 1 to 7 carbon atoms,benzyl,

and R NHCOCH where R is hydrogen or alkyl having 1 to 4 carbon atoms; or

b. together part of a morpholinium or piperidinium moiety;

R is a lipophilic aliphatic hydrocarbon group having from about 7 toabout 28 carbon atoms including saturated, unsaturated, straight-chainand branched groups,

and mixtures thereof; and

X" is halide, e.g., fluoride, chloride, bromide, or iodide;

alkyl sulfate wherein the alkyl moiety has 1 to 4 carbon atoms, ortoluene sulfonate.

The monomeric emulsion stabilizers having the formula I can besynthesized by several convenient methods. For

example, according to one process an alkyl or alkenyl succinic anhydrideis reacted with a tertiary-amino alcohol or amine, to provide anintermediate which is subsequently reacted with a monomer containing anactive halogen atom to provide compounds I wherein X'- is halide. Thisreaction is illustrated by the following general equation wherein V, R,R, A, and R are as previously described.

Exemplificative tertiary-amino alcohols and amines II suitable for usein the preparation of compounds I include dimethylaminoethanol,methylpropylaminopropan01, dibutylamino isopropylamine,dimethylaminoacetoxypropanol and hydroxypropyl piperidine.

The alkyl or alkenyl succinic anhydrides HI are readily provided byknown methods, such as by reacting maleic anhydride with an olefin asdescribed in US. Pat. 2,741,- 597. Illustrative compounds III includeheptenyl succinic anhydride, octacosasuccinic anhydride, n-heptylsuccinic anhydride, iso-octadecenyl succinic anhydride, etc.

Representative monomers having the formula VR'X include 2-bromoethylacrylate, 2-chloroethylacrylamide, allyl chloroacetate, methallylchloroacetate, acryloyloxypropenyl chloride, 3-methacryloyloxy,2-hydroxypropylene chloride, acryloyloxydi(ethylenoxy)ethylene chloride,allyl bromide, methallyl chloride, etc.

The reaction to provide the monomeric emulsion stabilizers I isgenerally carried out at temperatures from about C. to about 100 C., buthigher or lower temperatures can be employed. Preferably, temperaturesbetween about 25 C. and about 100 C. are used.

Although the reaction proceeds readily in the absence of a solvent,diluents such as water, acetonitrile, dimethylformamide, ethyl acetate,methanol and methylene chloride can be suitably employed. Monomers suchas acrylonitrile can also be utilized as solvents in the preparation ofthe monomeric emulsion stabilizers. While compounds I can be isolatedprior to use in polymerization reactions, preferably they are used intheir reaction solutions.

Alternately, the above-described process can be reversed by firstquaternizing the tertiary-amino compound U by the monomer VR"X, followedby reaction with the alkyl or alkenyl succinic anhydride III.

Another suitable method for preparing the monomeric emulsion stabilizershaving the formula I wherein X- is halide comprises quaternizing a vinylmonomer containing a tertiary-amine group by a halo-alcohol or amine,followed by reaction with the alkyl or alkenyl succinic anhydride inaccordance with the following general 4 equation wherein V, R, R, A, R RR and X- are as first described.

Again, as in the first process, the order of the above reaciton can bereversed.

A third general procedure for the preparation of compounds I comprisesthe reaction of an alkyl or alkenyl succinic anhydride with a vinylcontaining tertiary amino alcohol or amine followed by quaternization asillustrated by the following equation. All compounds included in formulaI can be prepared by this method with the exception of those monomericemulsion stabilizers wherein R and R together are part of a morpholiniumor piperidinium moiety.

For example, vinyl containing tertiary amino alcohols such asallylbenzylaminoethanol; 4-hydroxymaleoylaminoethyl,Z-aminOethylmethylamine; etc. can be employed as starting materials inthis process. Suitable quaternizing agents include dimethyl sulfate,dibutyl sulfate, methyl toluene sulfonate, ethylchloroacetate,propylchloroacetate, chloroacetamide, methyl bromide, bromoethanol,bromoheptanol, etc.

All compounds I wherein X- is alkyl sulfate in which the alkyl moietyhas 1 to 4 carbon atoms, or toluene sulfonate can be provided byreacting the corresponding quaternary ammonium halide with anappropriate alkali metal salt, e.g. sodium methyl sulfate, sodium butylsulfate, sodium toluene sulfonate, etc.

Particularly preferred monomeric emulsion stabilizers include thosecompounds I wherein V is allyl, methallyl, vinylacetoxy, allylacetoxy ormethallylacetoxy; R is zero; R is ethylene, propylene or isopropylene; Ais oxygen or -NH-; R and R are (a) independently selected alkyl having 1to 4 carbon atoms, or (b) together part of a morpholinium orpiperidinium moiety; R is a lipophilic aliphatic hydrocarbon grouphaving about 7 to about 28 carbon atoms; and X- is halide; and compoundsI wherein V is acryloyloxy, methacryloyloxy, vinyloxy, or4-hydroxymaleoyl; R and R are independently selected ethylene, propyleneor isopropylene groups; A is oxygen; R and R are (a) independentlyselected alkyl having 1 to 4 carbon atoms; or (b) together part of amorpholinium or piperidinium moiety; R is a lipophilic aliphatichydrocarbon group having from about 7 to 28 carbon atoms; and X- ishalide.

The monomeric emulsion stabilizers described in this invention are a newand exceptionally efficient species, promoting the smooth and readypolymerization of a wide variety of ethylenically-unsaturated monomers.

Illustrative ethylenically-unsaturated monomers suitable forcopolymerizing with the monomeric emulsion stabilizers of this inventioncomprise vinyl acetate, vinyl chloride, acrylonitrile, and acrylicmonomers in general represented by the formula where R is a hydrogenatom or a methyl group, and R is an alkyl radical of 1 to 14, andpreferably 1 to 4 carbon atoms. As is known in the art of preparingacrylic ester polymers, the softness of the polymer and the difficultyof initiating polymerization increase as the number of carbon atoms inthe ester group increases. In the practice of this invention, when theacrylic monomer contains more than 8 carbon atoms in the ester group, itis advantageous to mix therewith at least about 20 mole percent of anacrylic ester with fewer than 4 carbon atoms in the ester group toinitiate polymerization and enhance the stability of the dispersion.

Mixtures of more than one such ethylenically-unsaturated monomer may beused, and in order to impart special properties of toughness, rigidity,or cross-linking reactivity to the polymer, a minor proportion, usuallyless than 20 mole percent, of the major monomer may be replaced by someother ethylenically-unsaturated monomer such as vinyl esters, typifiedby vinyl laurate and vinyl stearate; vinyl ethers such as vinyl methylether, vinyl ethyl ether, and vinyl butyl ether; di-unsaturated monomerssuch as diethylene glycol diacrylate, ethylene glycol diitaconate,diallyl phthalate, divinyl benzene and the like; acrylic and methacrylicacids, acrylamide and methacrylamide, hydroxyethyl acrylate andmethacrylate, and hydroxypropyl acrylate, and methacrylate, and styrene.

In general, in the polymerization process of this invention, 0.1 to 10percent by weight of monomeric emulsion stabilizer is employed, with lto 5 percent by weight being preferred. The amount of monomeric emulsionstabilizer is based on the total monomers added to the polymerizationreaction.

Aqueous polymeric dispersions may be prepared according to thisinvention in which the solid polymer content is 40% to 50% by weight. Ifdesired, the solids content may be diluted to 1% by weight or less, withexcellent retention of stability at both the higher and lowerconcentrations.

The monomeric emulsion stabilizers of this invention are useful in bothbatch and continuous polymerization processes.

The following examples will serve to illustrate the practice of thisinvention.

EXAMPLE 1 Allyl chloride (7.7 g.) was added gradually at 25 C. to asolution of 8.9 g. of dimethylaminoethanol in 16.6 g. of acetonitrile.The resulting clear solution was maintained at 25 C. for 25 hours; atthe end of this period the solution had crystallized. Then 21.1 g. ofoctenyl succinic anhydride was added to the crystallized mixture and theresulting mixture heated at 50 C. for 5 hours to provide a homogeneoussolution. The solvent was removed under vacuum, thereby providing adark, orange-brown viscous liquid. Potentiometric titration for carboxylion confirmed that allyl dimethyl octenylhydroxysuccyloxyethyl ammoniumchloride had been obtained.

Ethyl acrylate (120 g.), butyl acrylate g.) and acrylonitrile (15 g.)were charged to a 4-neck resin kettle equipped with a thermometer,stirrer, nitrogen inlet and dropping apparatus. To the amount of 4.5 g.of the monomeric emulsion stabilizer described in the precedingparagraph, dissolved in 425 g. of H 0, was added, under nitrogen, themixture of monomers. The pH of the resulting emulsion was 4.04.5. Aftercooling to C. by the use of an ice bath, 15 ml. of 3% H 0 in H 0 wereadded to the emulsion followed by dropwise addition of a reductantsolution comprising 0.02 g. ferrous ammonium sulfate and 0.4 g. ascorbicacid in 10 ml. H O. Polymerization was initiated after 2.5 ml. ofreductant solution had been added as evidenced by an exotherm of about29 C. in 10 minutes. A total of 9 ml. of reductant solution was addeduntil completion of the polymerization as evidenced by a lack ofexotherm upon the further addition of a slight amount of H 0 andreductant. The yield of polymer was 95% of theoretical, and no coagulumformed.

EXAMPLE 2 Following the procedure of Example 1, 7.7 g. of allyl chloridewas added slowly, with stirring, to a solution of 8.9 g. ofdimethylaminoethanol in 16.6 g. of acetonitrile. The reaction solutioncrystallized after standing 24 hours at room temperature. Then asolution of 26.7 g. of ndodecenyl succinic anhydride in 26.7 g. ofacetonitrile was added and the mixture maintained at 50 C. for 5 hours,thereby providing a clear homogeneous solution. The solvent was removedunder vacuum to yield a viscous orange liquid. Potentiometric titrationfor carboxyl ion confirmed that allyl dimethyln-dodecenylhydroxysuccinyloxyethyl ammonium chloride had been obtained.

EXAMPLE 3 Dimethylaminoethanol (102 g.) was added slowly at 17 C. to asolution of 88.3 g. of allyl chloride in 500 g. of acrylonitrile. Overminutes an exotherm of 26 C. was observed. Then the solution was allowedto cool to 35 C. at which temperature crystallization occurred,producing a 10 C. exotherm. Tetrapropenyl succinic anhydride, which isan alkenyl succinic anhydride having an average of 12 carbon atoms andone carbon-carbon double bond (310 g.), was added to the crystallizedmixture; after 45 minutes a clear, homogeneous solution was obtained.This solution was allowed to stand for 48 hours. Chloride ion analysisconfirmed that allyl dimethyl tetrapropenylhydroxysuccinyloxyethylammonium chloride had been obtained.

EXAMPLE 4 Dimethylaminoethanol (35.6 g.) Was added slowly to a solutionof 106.4 g. of tetrapropenyl succinic anhydride in 160 ml. of ethylacetate. After completion of the exotherm, a dark orange liquid wasobtained. Allyl bromide (12.1 g.) was added to 65.5 g. of this liquid.After the mixture was allowed to stand for 24 hours at room temperature,bromide ion analysis confirmed that allyl dimethyltet-rapropenylhydroxysuccinyloxyethyl ammonium bromide had beenobtained.

The amount of 4 g. of this compound was dissolved in 290 g. of H 0 and75 g. of ethyl acrylate added; the pH of the resulting emulsion wasabout 5. After cooling to 19 C., polymerization was initiated andmaintained by the addition of 8 ml. of 3% H 0 in H O followed by thedropwise addition of the reductant solution described in Example 1. Atotal of 2.9 ml. of reduction solution was employed in thepolymerization and the yield of polymer was of theoretical.

EXAMPLE 5 A solution of 29.5 g. of n-tetradecenyl succinic anhydride in29.5 g. of acetonitrile was added to the reaction product of 8.9 g. ofdimethylaminoethanol and 7.7 g. of allyl chloride in 16.6 g. ofacetonitrile as described in Example 1, and the resulting mixture heatedat 55 C. for 4 hours. Removal of solvent under vacuum provided 42.6 g.of greasy, oil-white solid. Carboxyl ion analysis confirmed that allyldimethyl n-tetradecenylhydroxysuccinyloxyethyl ammonium chloride hadbeen obtained.

EXAMPLE 6 Following the procedure of Example 5, 35.6 g. ofisooctadecenyl succinic anhydride was added to the reaction product ofdimethylaminoethanol and allyl chloride in acetonitrile. After 5 hoursat 55 C., solvent was removed under vacuum to provide an orange viscousliquid. Analysis for carboxyl ion content confirmed that allyl dimethyliso octadecenylhydroxysuccinyloxyethyl ammonium chloride had beenobtained.

A mixture of 120 g. of ethyl acrylate, 15 g. of butyl acrylate and 15 g.of acrylonitrile in 425 g. of H was emulsified employing 4.5 g. of theallyl dimethyl isooctadecenylhydroxysuccinyloxyethyl ammonium chloride.The emulsion, which had a pH of 4.5-5.0, was cooled to slightly belowroom temperature. Then 15 ml. of 3% H 0 solution was added followed bythe dropwise addition of the reductant solution described in theprevious examples. A total of 7 ml. of reductant solution was used inthe polymerization; no coagulum formed and the yield of polymer was 93%of theoretical.

EXAMPLE 7 A solution of 71.2 g. of iso-octadecenyl succinic anhydride in52 g. acetonitrile was added slowly to a 50% solution of 18 g.dimethylaminoethanol in acetonitrile at 25 C. The reaction wasexothermic and two layers formed. After stirring the reaction mixturefor one hour at 25 C., the temperature was raised to 40-50 C. and thereaction mixture heated for one and one-half hours. Solvent removl undervacuum provided a viscous orange liquid. To a solution of 22.3 g. ofthis orange liquid in 28.4 g. of dimethylformamide was added 6.07 g. ofallyl bromide at 25 C. After 24 hours, bromide ion analysis indicatedthat allyl dimethyl iso-octadecenylhydroxysuccinyloxyethyl ammoniumbromide had been obtained.

EXAMPLE 8 -Dimethylaminoethanol (8.9 g.) was added to 9.06 g. ofmethallyl chloride in 44.6 g. of acetonitrile. After allowing themixture to stand for 24 hours at room temperature, a clear homogeneoussolution was obtained. Upon the addition of 26.6 g. of tetrapropenylsuccinic anhydride, an exothermic reaction occurred. Solvent was removedunder vacuum to provide a viscous liquid product. Analysis for carboxylion content confirmed that methallyl dimethyltetrapropenylhydroxysuccinyloxyethyl ammonium chloride had beenobtained.

EXAMPLE 9' Vinyl chloroacetate (6.02 g.) was added to the reactionproduct of 4.5 g. of dimethylaminoethanol and 17.8 g. ofiso-octadodecenyl succinic anhydride in 27 g. of dimethylformamide.After allowing the reaction mixture to stand for 24 hours at roomtemperature, a homogeneous solution was obtained. Chloride ion analysisconfirmed that vinylacetoxy dimethyl isooctadecenylhydroxysuccinyloxyethyl ammonium chloride had been obtained.

A mixture of 120 g. of ethyl acrylate, 15 g. of butyl acrylate and 15 g.of acrylonitrile was emulsified with 425 g. H 0 and 6.6 g. of thevinylacetoxy dimethyl isooctadecenylhydroxysuccinyloxyethyl ammoniumchloride solution (68 percent by weight in dimethylformamide). Theresulting emulsion, having a pH of 4.5, was cooled to about 18 C.Polymerization was initiated by the addition of 15 ml. of 3% H 0 in H Ofollowed by the dropwise addition of 2.2 ml. of the reductant solutiondescribed in the previous examples. A total of 8 ml. of reductantsolution was employed in the polymerization. No coagulum was formed andthe yield of polymer was 94% of theoretical.

EXAMPLE A solution of 53.2 g. of tetrapropenyl succinic anhydride inacetonitrile was added slowly with stirring, at 25 C., to a solution of20.4 g. of dimethylaminopropylamine in acetonitrile; a total of 73.6 g.of acetonitrile was employed. After stirring the reaction mixture fortwo hours at room temperature, the solvent was removed under vacuum toprovide 71.5 g. of orange viscous liquid. Then a solution of 6.05 g. ofallyl bromide in 24.5 g. of acetonitrile was added to 18.4 g. of theorange viscous liquid. The resulting mixture was allowed to stand atroom temperature for 5 days. Removal of the solvent under vacuumprovided 23.9 g. of orange-brovm viscous liquid. Bromide ion analysisconfirmed that allyl dimethyl tetrapropenylhydroxysuccinylaminopropylammonium bromide had been obtained.

A mixture of 120 g. of ethyl acrylate, 15 g. of butyl acrylate and 15 g.of acrylonitrile in 425 g. of H 0 was emulsified using 4.5 g. allyldimethyl tetrapropenylhydroxysuccinylaminopropyl ammonium bromide. Theresulting emulsion, having a pH of 4.5-5.0, was cooled to 18 C.Polymerization was initiated by the addition of 15 ml. of 3% H 0 in H Ofollowed by the addition of 1.5 ml. of the reductant solution describedin the previous examples. A total of 7 ml. of reductant solution wasrequired to complete the polymerization. No coagulum formed and theyield of polymer was 92% of theoretical.

EXAMPLE 11 The amount of 20.4 g. of dimethylaminopropylamine was addedto 15.3 g. of allyl chloride dissolved in 35.7 g. of acetonitrile. Thereaction was carried out at icebath temperature. After 24 hours at roomtemperature, 53.2 g. of tetrapropenyl succinic anhydride was addedslowly, with stirring, to the reaction solution. Solvent removalprovided a product which contained 96% of the theoretical carboxyl ioncontent of allyl dimethyl tetrapropenylhydroxysuccinylaminopropylammonium chloride had been obtained.

EXAMPLE 12 Dimethylaminoethyl methacrylate (15.7 g.) was added, withstirring, at room temperature to a solution of 12.5 g. of 2-bromoethanolin 28.2 g. of acetonitrile. A slightly exothermic reaction ensued. Thereaction solution was allowed to stand for 4 days. Then 26.6 g. oftetrapropenyl succinic anhydride was added to the solution. A slightlyexothermic reaction occurred. After allowing the reaction mixture tostand at room temperature for 24 hours, carboxyl ion analysis revealedthat methacryloyloxyethyl dimethyl tetrapropenylhydroxysuccinyloxyethylammonium bromide had been obtained.

To 4.5 g. of the above monomeric emulsion stabilizer solution (66percent by weight in acetonitrile) was added 100 g. of ethyl acrylateand 290 g. of H 0. The resulting emulsion, having a pH of 4.5, wascooled to 17 C. and polymerization initiated by the addition of 10 ml.3% H 0 solution followed by 2 ml. of the reductant solution described inthe previous examples. A total of 3 m1. of reductant solution wasemployed in the polymerization. No coagulum formed and the yield ofpolymer was of theoretical.

EXAMPLE 13 Following the procedure of Example 12, 11.5 g. ofdimethylaminoethyl vinyl ether was added at room temperature to asolution of 12.5 g. of 2-bromoethanol in 24.3 g. of acetonitrile. Thereaction was slightly exothermic. After allowing the reaction mixture tostand at room temperature for 4 days, a clear, homogeneous solution wasobtained. To this solution was added 26.8 g. of tetrapropenyl succinicanhydride. After allowing this reaction mixture to stand at roomtemperature for 48 hours, carboxyl ion analysis indicated thatvinyloxyethyl dimethyl tetrapropenylhydroxysuccinyloxyethyl ammoniumbromide had been obtained.

EXAMPLE 14 Allyl chloroacetate (6.73 g.) was added to the reactionproduct of 4.5 g. of dimethylaminoethanol and 17.8 g. ofiso-octadodecenyl succinic anhydride in 27 g. of dimethyl formamide.Chloride ion analysis confirmed that allylacetoxy dimethyliso-octadecenylhydroxysuccinyloxyethyl ammonium chloride had beenobtained.

9 EXAMPLE 15 A solution of 26.6 g. of tetrapropenyl succinic anhydridein 25 g. dimethyl formamide was added slowly with stirring, at 25 C. toa solution of 13.1 g. of hydroxyethylmorpholine in 20 g. dimethylformamide. The reaction was exothermic, providing a light, orange-brownhomogeneous solution which contained 93% of the theoretical carboxyl ioncontent. Allyl bromide (10.9 g.) was added to the solution and theresulting mixture allowed to stand at room temperature for 6 days.Bromide ion analysis confirmed that allyltetrapropenylhydroxysuccinyloxyethyl morpholinium bromide had beenobtained.

EXAMPLE 16 A solution of 26.6 g. of tetrapropenyl succinic anhydride in25 g. dimethylformamide was added slowly, with stirring, at 25 C. to asolution of 8.9 g. of dimethylaminoethanol in 10 g. ofdimethylformamide. The reaction Was exothermic, providing, after 24hours, a clear homogeneous solution which contained 100% of thetheoretical carboxyl ion content. To the above solution was added, at 25C. with stirring, an equimolar amount of Z-bromoethanol. The reactionwasslightly exothermic. After allowing the reaction mixture to stand forfive days at 25 C. and then for 3 /2 hours at 4550 C., 82% of thetheoretical bromide ion content was determined. To this solution wasadded an equimolar amount of maleic anhydride; the addition was carriedout with stirring at room temperature. After 24 hours at roomtemperature, carboxyl ion analysis indicated that 2 (4hydroxymaleoyl)-oxyethyldimethyltetrapropenylhydroxysuccinyloxyethylammonium bromide had been obtained.

What is claimed is:

1. A compound having the formula wherein V is an ethylenicallyunsaturated radical selected from the group consisting of acryloyloxy,methacryloyloxy,

acrylamido, methacrylamido, vinyloxy, allyloxy, methallyloxy,4-hydroxymaleoyloxy, 4-hydroxyfumaroyloxy, 4-hydroxycitraconyloxy or4-hydroxyitaconyloxy;

R and -R" are independently selected ethylene, propylene, isopropylene,Z-hydroxypropylene, acetoxypropylene or --'O'--cH2-CHR4(OCHz-CHR4) Wheren is zero to 4 and R is hydrogen or methyl;

A is oxygen;

R and R are independently selected from the group consisting of alkylhaving 1 to 7 carbon atoms, hydroxyalkyl having 1 to 7 carbon atoms orbenzyl;

R is a lipophilic aliphatic hydrocarbon group having from 7 to 28 carbonatoms; and

X- is halide or toluene sulfonate.

2. The compound of Claim 1 wherein V is acryloyloxy, methacryloyloxy,vinyloxy, 4-hydroxymaleoyl; R and R are independently selected ethylene,propylene or isopropylene groups;

A is oxygen;

R and R are independently selected alkyl having 1 to 4 carbon atoms;

R, is a lipophilic aliphatic hydrocarbon group having from 7 to 28carbon atoms; and

X- is halide.

3. The compound of Claim 2 having the name N-methacryloylethyl N,Ndimethyl-N-(tetrapropenylhydroxysuccinyloxyethyl) ammonium bromide.

4. The compound of Claim 2 having the name N vinyloxyethyl N,Ndimethyl-N-(tetrapropenylhydroxysuccinyloxyethyl) ammonium bromide.

5. The compound of Claim 2 having the name N-[2-(4-hydroxymaleoyl)-oxyethyl] N,Ndimethyl-N-(dodecenylhydroxysuccinyloxyethyl) ammonium bromide.

References Cited UNITED STATES PATENTS 3,288,770 11/1966 Butler 260-883LORRAINE A. WEINBERGER, Primary Examiner E. J. SKELLY, AssistantExaminer U.S. Cl. X.R.

260-2472 B, 485 G, 485 J

1. A COMPOUND HAVING THE FORMULA